CN110208326A - Work in the preparation method of the metal composite oxide base ethyl alcohol gas sensor under low temperature - Google Patents

Work in the preparation method of the metal composite oxide base ethyl alcohol gas sensor under low temperature Download PDF

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Publication number
CN110208326A
CN110208326A CN201910557577.5A CN201910557577A CN110208326A CN 110208326 A CN110208326 A CN 110208326A CN 201910557577 A CN201910557577 A CN 201910557577A CN 110208326 A CN110208326 A CN 110208326A
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zno
tio
gas sensor
preparation
ethyl alcohol
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王秀宇
徐雯
冷彬心
陶涛
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Tianjin University
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Tianjin University
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means

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Abstract

The present invention discloses a kind of preparation method of metal composite oxide base ethyl alcohol gas sensor worked under low temperature, first passes through coprecipitation preparation ZnSn (OH)6Presoma uses nano-TiO2It is modified with ZnO doping, TiO is obtained after high-temperature calcination2‑ZnO@ZnSnO3Composite powder.The present invention provides a kind of preparation methods of metal composite oxide base ethyl alcohol gas sensor that can be worked under lower temperature, are reducing ZnSnO3Higher air-sensitive response and faster response/recovery are obtained while gas sensor operating temperature.

Description

Work in the preparation of the metal composite oxide base ethyl alcohol gas sensor under low temperature Method
Technical field
It is the invention belongs to semiconductor gas sensor field, in particular to a kind of to work at a lower temperature and gas sensing property The excellent metal composite oxide base ethyl alcohol gas sensor preparation method of energy.
Background technique
The rapid development of modern industry, many organic chemical substances (such as methanol, ethyl alcohol, formaldehyde, acetone) are many Industry has a wide range of applications, these substances also bring certain peace while to people's lives, work belt to facilitate Full hidden danger, for example, will lead to serious ring when certain toxic or inflammable and explosive substance leaks during the work time Border and safety problem.Ethyl alcohol as a kind of inflammable, volatile unary alcohol compound, the fields such as medicine, agricultural, chemical industry all There is important application, how to carry out real-time, effectively detection and monitoring to it in process of production just becomes Important Problems.Base It is raw in industry in cost is relatively low because of it, easily prepared, response is fast for the gas sensor of metal oxide semiconductor material the advantages that The fields such as production, environmental monitoring, ecological protection are widely used, and become the hot topic currently studied both at home and abroad.
Binary metal oxide ZnO and SnO2It is the wide bandgap semiconductor gas sensitive of early start research, has nontoxic Environmental protection, the advantages that cost is relatively low, high sensitivity, their composite oxides zinc metastannate (ZnSnO3) it is a kind of with perovskite The ternary composite metal oxide semiconductor of structure, air-sensitive performance have both ZnO and SnO2The advantages of two kinds of materials, but it is pure ZnSnO3In the presence of with ZnO, SnO2Same problem, when obtaining maximum air-sensitive response, corresponding operating temperature is higher, usually exists 200 DEG C or more, the monitoring to the hazardous gases such as inflammable, explosive is not suitable for.Therefore, how ZnSnO is effectively reduced3Air-sensitive passes The optimum working temperature of sensor becomes the emphasis of this field research.To solve the above problems, the present invention selects nano-TiO2With Two kinds of ultraviolet light-sensitive materials of ZnO, to pure ZnSnO3Modification is carried out, improves it while reducing its optimum working temperature Air-sensitive performance.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of composition metal oxidations worked under low temperature The preparation method of object base ethyl alcohol gas sensor.
The preparation method for working in metal composite oxide base ethyl alcohol gas sensor under low temperature, first passes through co-precipitation legal system Standby ZnSn (OH)6Presoma uses nano-TiO2It is modified with ZnO doping, TiO is obtained after high-temperature calcination2-ZnO@ZnSnO3It is compound Object powder.
The present invention provides a kind of preparation sides of metal composite oxide base ethyl alcohol gas sensor worked under low temperature Method is reducing ZnSnO3Higher air-sensitive response and faster response/recovery are obtained while gas sensor operating temperature.
The present invention is to solve the problems, such as to propose in background technique, the technical solution adopted is that the compound gold under working in low temperature The preparation method for belonging to oxide-base ethyl alcohol gas sensor includes the following steps:
1) according to Zn2+: Sn4+The stoichiometric ratio of=1:1, by SnCl4·5H2O and ZnSO4·7H2O is dissolved in dehydrated alcohol Middle formation mixed solution, then NaOH solution is added to adjust PH to mixed solution is 13, obtains white precipitate, through deionized water and After dehydrated alcohol washing, supernatant liquor is removed, is dried on 40 DEG C of drying stations, obtains presoma；
2) nano-TiO of different quality is successively weighed2, ZnO and ZnSn (OH)6Presoma mixing, is dissolved in deionized water Abundant slow magnetic agitation, combines it uniformly, obtains the combination product of different levels of doping after washing is dry；
3) combination product is placed in chamber type electric resistance furnace the high-temperature calcination under 500 DEG C of environment, to its cooled to room temperature After take out, obtain the TiO2-ZnO@ZnSnO3 compound of different levels of doping；
4) the TiO2-ZnO@ZnSnO3 compound prepared is mixed with deionized water, forms the paste of proper viscosity Object；
5) paste is coated on the potsherd for having golden interdigital electrode, makes its uniform fold.Sufficiently after drying, on potsherd It will form one layer of uniform sensitive membrane.
Above-mentioned steps 2) in, as doping nano-TiO2When concentration is m wt%, ZnO concentration is n wt%, gained compound Powder is denoted as STZm-n, wherein nano-TiO2、ZnO、ZnSn(OH)6Powder optimum quality ratio is 10:0.5:100, is denoted as STZ10-0.5。
The utility model has the advantages that the present invention provides a kind of metal composite oxide base ethyl alcohol air-sensitives that can be worked under lower temperature The preparation method of sensor is reducing ZnSnO3Higher air-sensitive response and faster is obtained while gas sensor operating temperature Response/recovery.
1, ultraviolet light has the nano-TiO on the potsherd of golden interdigital electrode2-ZnO@ZnSnO3Compound improves ZnSnO3The gas sensing mechanism of sensor makes it just have good air-sensitive performance under lower operating temperature.
2, the present invention is effectively reducing ZnSnO3While gas sensor optimum working temperature, its most atmosphere is improved Quick response simultaneously shortens response/recovery time.
Detailed description of the invention
Fig. 1 is prepared gas sensor schematic diagram in the present invention.
Fig. 2 is prepared TiO in the present invention2-ZnO@ZnSnO3The SEM of compound schemes.
Fig. 3 is the response curve graph of sensor under the conditions of ultraviolet lighting, 500ppm concentration ethanol at different temperatures.
Fig. 4 is sample of the present invention at 70 DEG C, to different concentration ethanol gas response characteristic curve under ultraviolet irradiation condition Figure.
Fig. 5 is air-sensitive performance of the sample of the present invention at 70 DEG C, when working under ultraviolet irradiation condition
(a) response-recovery characteristic curve of the sample in different concentration ethanol gaseous environment；
(b) response-recovery time histogram of the sample in different concentration ethanol gaseous environment.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
1) according to Zn2+: Sn4+The stoichiometric ratio of=1:1 configures SnCl4And ZnSO4Then NaOH solution tune is added in solution Saving PH is 13, obtains ZnSn (OH)6Presoma removes supernatant liquor, dries at 40 DEG C after deionized water and dehydrated alcohol washing It is dried on dry platform, obtains presoma；
2) nano-TiO of different quality is weighed2, ZnO and ZnSn (OH)6Presoma mixing, is dissolved in deionized water sufficiently Slow magnetic agitation, combines it uniformly, obtains the combination product of different levels of doping after washing is dry.
3) combination product is placed in chamber type electric resistance furnace the high-temperature calcination under 500 DEG C of environment, to its cooled to room temperature After take out, obtain the TiO of different levels of doping2-ZnO@ZnSnO3Compound.
4) TiO that will have been prepared2-ZnO@ZnSnO3Compound is mixed with deionized water, forms the paste of proper viscosity Object.Appropriate paste is coated on the potsherd for having golden interdigital electrode, makes its uniform fold.Sufficiently after drying, meeting on potsherd Form one layer of uniform sensitive membrane.
5) the air-sensitive test method in referenced patent CN109187662A patent of invention, by air-sensitive made from step (4) Sensing element is placed on test platform, gas sensor element is connect 100V voltage, LED ultraviolet lamp connects 5V voltage, opening electricity Source switch, prepared sensor can work.
Test result shows: in experimental procedure 2) in, work as TiO2, ZnO and ZnSn (OH)6When mass ratio is 10:0.5:100, Air-sensitive experiment effect is best, which rings under ultraviolet irradiation condition, to 500ppm ethanol gas concentration at 70 DEG C It should value Ra/RgReach maximum, is 75.82, as shown in Figure 3；70 DEG C, the gas sensor is in different ethyl alcohol under ultraviolet irradiation condition Shown in response-recovery characteristic such as Fig. 5 (a) under gas concentration, and when ethanol gas concentration is 10ppm, prepared air-sensitive Sensor response and recovery time are respectively 2s and 7s, as shown in Fig. 5 (b).
In conclusion preparing ZnSn (OH) with coprecipitation6Hollow cube is as presoma, with different quality ratio nano-TiO2It modifies with ZnO codope, then gained compound is placed in resistance furnace with natural after 500 DEG C of high-temperature heat treatments It is cooled to room temperature, obtains TiO2-ZnO@ZnSnO3Compound, STZ10-0.5 compound show good air-sensitive to alcohol gas Characteristic.This compound possesses good gas-selectively, stability, shorter response and recovery time simultaneously, can be effectively reduced ZnSnO3The operating temperature of gas sensor, makes it just have good air-sensitive performance at a lower temperature, and this method can push away It is wide to be applied to prepare other low temperature gas sensors.

Claims (3)

1. the preparation method of the metal composite oxide base ethyl alcohol gas sensor under working in low temperature, which is characterized in that first lead to Cross coprecipitation preparation ZnSn (OH)6Presoma uses nano-TiO2It is modified with ZnO doping, TiO is obtained after high-temperature calcination2- ZnO@ZnSnO3Composite powder.
2. the preparation method of the metal composite oxide base ethyl alcohol gas sensor under low temperature is worked according to requiring 1, It is characterized by comprising the following steps:
1) according to Zn2+: Sn4+The stoichiometric ratio of=1:1, by SnCl4·5H2O and ZnSO4·7H2O is dissolved in shape in dehydrated alcohol At mixed solution, then NaOH solution is added to adjust PH to mixed solution is 13, white precipitate is obtained, through deionized water and anhydrous After ethanol washing, supernatant liquor is removed, drying obtains presoma；
2) nano-TiO of different quality is successively weighed2, ZnO and ZnSn (OH)6Presoma mixing, is dissolved in deionized water sufficiently Slow magnetic agitation, combines it uniformly, obtains the combination product of different levels of doping after washing is dry；
3) it by combination product high-temperature calcination, is taken out after its cooled to room temperature, obtains the TiO of different levels of doping2-ZnO@ ZnSnO3Compound；
4) TiO that will have been prepared2-ZnO@ZnSnO3Compound is mixed with deionized water, forms the paste of proper viscosity；
5) coating step 4 on the potsherd for having golden interdigital electrode) gained paste, make its uniform fold, sufficiently after drying, pottery One layer of uniform sensitive membrane is formed on tile.
3. the preparation method of the metal composite oxide base ethyl alcohol gas sensor under low temperature is worked according to requiring 1, It is characterized in that, in the step 2), as doping nano-TiO2When concentration is m wt%, ZnO concentration is n wt%, gained is multiple It closes object powder and is denoted as STZm-n, wherein nano-TiO2、ZnO、ZnSn(OH)6Powder optimum quality ratio is 10:0.5:100, is denoted as STZ10-0.5。
CN201910557577.5A 2019-06-25 2019-06-25 Work in the preparation method of the metal composite oxide base ethyl alcohol gas sensor under low temperature Pending CN110208326A (en)

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CN110865034A (en) * 2019-10-22 2020-03-06 东北大学 Ethanol gas sensor based on tunable polymer micro-bottle
CN111077189A (en) * 2019-12-10 2020-04-28 天津大学 Preparation method of high-performance ethanol gas sensor working at low temperature
CN111257376A (en) * 2020-02-10 2020-06-09 天津大学 Preparation method of composite modified spherical zinc metastannate low-temperature gas-sensitive material
CN113189151A (en) * 2021-04-30 2021-07-30 重庆文理学院 High-response high-thermal-stability tin dioxide sensor and preparation method thereof
CN113189152A (en) * 2021-04-30 2021-07-30 重庆文理学院 Sensing equipment capable of detecting ethanol in high-temperature environment and processing method
CN114965651A (en) * 2022-05-19 2022-08-30 湖北大学 ZnO-based methane sensor and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110865034A (en) * 2019-10-22 2020-03-06 东北大学 Ethanol gas sensor based on tunable polymer micro-bottle
CN111077189A (en) * 2019-12-10 2020-04-28 天津大学 Preparation method of high-performance ethanol gas sensor working at low temperature
CN111257376A (en) * 2020-02-10 2020-06-09 天津大学 Preparation method of composite modified spherical zinc metastannate low-temperature gas-sensitive material
CN111257376B (en) * 2020-02-10 2022-05-03 天津大学 Preparation method of composite modified spherical zinc metastannate low-temperature gas-sensitive material
CN113189151A (en) * 2021-04-30 2021-07-30 重庆文理学院 High-response high-thermal-stability tin dioxide sensor and preparation method thereof
CN113189152A (en) * 2021-04-30 2021-07-30 重庆文理学院 Sensing equipment capable of detecting ethanol in high-temperature environment and processing method
CN114965651A (en) * 2022-05-19 2022-08-30 湖北大学 ZnO-based methane sensor and preparation method and application thereof

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